Printing paste



Patented Apr. 7, 1931 UNITED STATES PATENT OFFICE JEAN GEORGES KERN, OF WALTHAM, MASSACHUSETTS, AND CHARLES J'. SALA, OF WILMINGTON, DELAWARE, ASSIGNORS TO E. I. DU PONT DE NEMOURS & COMPANY OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE I PRINTING PASTE No Drawing. Original application filed August 4, 1927, Serial No. 210,714. Divided and this application filed March 21, 1930. Serial No. 437,941.

This case is a division of our copending application Serial No. 210,714, filed August 4, 1927.

This invention relates to alkylolamine salts of aliphatic acids both saturated and unsaturated and to the sulfonic acid derivatives of these acids and more particularly to the ethanolamine salts of the higher fatty acids.

This invention has as objects the preparation of soluble oils, solvents and detergents as well as of antiseptic soaps.

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more partioularl of the ethanolamines, by combination wit the fatty acids mentioned above by any of the well known methods for the production of salts.

The bases used for our purpose ma be represented by the following general ormula:

/A1k0H N-R1 where Alk represents an aliphatic or hydroxy aliphatic radical, R and R represent hydro en or an aliphatic radical or a hydroxy ali atic radical or a polyhydroxy aliphatic ra 'cal. In making these new soluble oils we r that the reaction is complete when a sample of the mixture dissolves entirely in water. If water is present at the start this may be driven off, the base not being volatile, until a concentrated product is left behind. When making these products by this method it is found that an excess of base is necessary to give the most satisfactory results.

When preparing the products obtained from the sulfonated fatty acids we may proceed as follows:

The acid product of the mixture of the sulfonated unsaturated acid as obtained by the action of sulfuric acid on an unsaturated oil such as castor oil in the well known manner is freed of mineral acid by washing. It is then freed of water either by settling or by any other suitable means and then enough of the alkylolamine base is added at ordinary temperature to neutralize the acidity of the sulfonic acid group or of both sulfonic acid and the carboxylic acid groups. The following examples will serve to illustrate our method of procedure, but it is to be understood that the invention is not to be limited thereby:

1 E mample 1 2823. 7 parts of tree oleic acid are mixed with I 1490 parts of tri-ethanolamine.

Example 2 298.37 parts of ricinoleic acid C1 H ,(OH)C0OH are mixed with 105 parts di-ethanolamine.

The resultant product is a clear yellow oil,

very soluble in water.

Example 1;

372 parts castor oil are mixed with 260 parts tri-etlianolamine 200 parts water.

The above mixture is heated on the water bath for several hours. The saponification proceeds slowly and in order to make it complete within reasonable time it is of advantage to add an excess, for example 30% triethanolamine, above the quantity mentioned.

Example 5 284. 39 parts of stearic acid are melted. Into the melt are stirred 149 parts tri-ethanolamine,-stirring is continued at a temperature of about 80 C. until the mixture is uniform.

The resultant product on cooling is a solid, not very soluble in water but very soluble in alcohol. It acts as an excellent assistant in promoting solution.

Example 6' 282 parts oleic acid 91 parts of amino-propane diol NHg- CHg-CH- CHg- OH are heated together until completely mixed. The product is very soluble in alcohol. In water the solution is cloudy but becomes clear on the addition of some excess base, e. g. 15 to 20%.

Example 7' 6 parts of a crude sulphonated oil made by the action of sulfuric acid on castor oil are mixed with 1 part of mono-ethanoiamine Example .9

2. 7 parts of a crude sulphonated oil mixture in the form of free acids are mixed with 1 part of a mixture of diand tri-ethanolamine.

The products of Examples 8 and 9 are entirely soluble in water. They are thick yellow oils resumably containing salts of the bases of t e sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The roducts formed in this way are quite satisactory for ordinary purposes.

In dyeing Ponsol blue GD double paste, Schultz No. 842, on cotton yarn in the package machine, using 5% of color, 2 sodium hydroxide, 3% hydrosulfite, theaddition of 1% of the product formed by combining 1 mole of sulfo-ricinoleic acid and 1 mole t'riethanolamine, containing di-ethanolamine, results in a brighter, more level dyeing.

The use in dying of the new compounds described in this case can be illustrated by the following example:

Example 10 a An 8.5% dyeing cf Ponsol blue' G Schultz No. 842, on 150 pounds of mercerized cotton piece goods is obtained as follows:

12.75 pounds Ponsol blue GD, Schultz No. 842, are mixed with 8.16 pounds of one of the compounds described in the examples of this case; 1 gallon of cold water is added and the suspension passed through a fine screen. A perfect speckless paste is thus obtained, which is added to the jigger dye bath composed of the following:

10 pounds caustic soda 15 pounds hydrosulfite concentrated, 10 pounds being added immediately and 5 pounds being added after one passage of the goods 100 gallons of water.

The temperature is raised to 110 F., and after complete reduction the dyeing started at this temperature. The temperature is then allowed to rise during 30 minutes to 125 0., and further dyed at this temperature for 10 to 15 minutes. Then give 1 wash, 4 passages in sodium perborate, 2 lbs. per 100 gals. at 120 F., 2 cold washes, 5 passes in boiling soap solution 3 lbs. soap to 100 gallons, then rinse and wash in the open, dry and calender.

This example, illustrating the methodof dyeing, is similar to Example 1 given in co-pending application Serial No. 210,715, filed by applicants on August 4:, 1927. The diiierence between this example and the said Example 1 lies in the substitution of the novel assistants herein disclosed by applicants.

Example 11 The new compounds described in this application may be used as assistants in the making of vat color pastes in a manner similar to the pastes described in applicants patented application bearing Patent Number 1,705,118, granted March 19, 1929. The dyestufi paste, as produced in the course of manufacture of Ponsol blue GD, Schultz N o. 842, is converted into a press cake containing 30% of dry color. 400 parts of the press cake are then mixed with 20 parts of glycerine and 580 parts of one of the assistants prepared according to Examples 1 to 9 and Example 13 of this application. It is possible to vary the quantities considerably without losing the advantages of this invention.

Example 152 vThe new compounds described in this case may be used in printing pastes containing lakes of basic colors. The mode of procedure in using such a printing paste is illustrated in the following example:

10 parts basic color (suitable for discharge printing) 50 parts glycerine 50 parts of any one of the products described in Examples 1 to 9 and Example 13 of this application 250 parts water 580 parts thickening composed of starch or gums and a certain amount of sodium hydrosulfite-formaldehyde necessary to cut the ground paris fiapnin dissolved in equal parts of water or a co 0 a usual. The process of printing illustrated in this example is identical with Example 4 in applicants co-pending case Serial No. 195,579, filed May 31, 1927, except for the insertion of the new assistants which comprise part of applicants herein disclosed invention.

E wample 13 If a pure product is needed the operation may be carried out as follows:

378 parts of pure suIfo-ricinoleic acid prepared by the action of chl0r0-sulf0nic acid on pure ricinoleic acid are mixed with 149 parts of tri-ethanolamine.

In the above case the addition of a further molecular equivalent of base produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again this point has not been determined.

In the above examples any one of the bases as defined by the general formula given above may be used either alone or in mixture. The fatty acids may also be varied through a wide range.

By the term alkylol, as used herein, we mean to include an alkyl radical in which one or more hydrogens are replaced by a hydroxyl group, and may be represented by the following:

G H OH or- C H -1 (OH) 2.

We have found that these products, which are essentially organic soaps possess a greater dissolving power or dispersing power for organic substances than do ordinary soaps. They possess the detergent property of soaps without the high alkalinity characteristic of sodium or potassium salts of the fatty acids. These products for these reasons have a distinct advantage for many purposes and particularly as assistants in dyeing, and those compounds which are derived from sulfonated castor oil by the process mentioned are in many ways superior to ordinary sulfonated oils. Their superiority is evidenced by the greater evenness of the shades developed, the better utilization of the color, and the greater brillance of the dyeing.

When'added to water they bring about solution or dispersion in so fine a form as to appear a solution of insoluble organic bases such as amino-azo-benzene, para-nitro-benzene, azo-diphenylamine, benzene-azo-naphthalene-azo-phenol, Rosanthrene base, di ethyl para amido phenol 1 :4 naphthoquinone-mono-imide, 2:4 di-nitro-benzene-lazo-di-ethyl-aniline, etc. It takes about 2 to 5 parts of the solvent for 1 part of the insoluble base. These solutions may be used very successfully for the purpose of dyeing fibers of esterified cellulose.

It has also been found that these soaps dissolve metallic hydroxides and oxides, for example, mercuric oxide, and this property indicates their probable value in pharmacology, for example, in the production of antiseptic soaps and the like.

As many apparently widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not intend to limit ourselves to the specific embodiments thereof except as indicated in the appended claims.

We claim:

1. A printing paste which contains a lake of a basic color and an alkylolamine salt of a higher fatty acid.

2. A printing paste which contains a. lake of a basic color and an ethanolamine salt of a higher fatty acid.

3. A printing paste which contains a lake of a basic color and an alkylolamine salt of an acid from the group consisting of oleic,

' stearic and ricinoleic acids.

4. A printing paste which contains a lake of a basic color and an ethanolamine salt of an acid from the group consisting of oleic,

stearic and ricinoleic acids.

5. A printing paste which contains a lake of a basic color and an alkylolamine salt of oleic acid.

6. A printing paste which contains a lake of a basic color and an ethanolamine salt of oleic acid.

7. A printing paste which contains a lake of a basic color and a salt formed by the chemical combination of di-ethanolamine and oleic acid.

8. A printing paste which contains a lake of a basic color and a higher fatty acid salt of a compound having the following formula Alk-OH the chemical combination of an acid from the group consisting of oleic, stearic and ricinoleic acids, together with a compound having the followlng formula:

/A1kOH N-R: \R: in which Alk represents an aliphatic or bydroxy aliphatic radical, while both R; and

R represent a monovalent substance from the group consisting of hydrogen aliphatic radicals hydroxy aliphatic radicals and polyhydroxy aliphatic radicals.

10. A printing paste which contains a lake of a basic color and a salt formed by the chemical combination of tri-ethanolamine and oleic acid.

11. A printing paste which contains a lake of a basic color and a salt formed b the chemical combination of mono-ethano amine and oleic acid.

In testimony whereof we afiix our signatures.

JEAN GEORGES KERN. CHARLES J. SALA. 

